Printing with vat colors



Paiented Get. 12, 1948 PRINTING WI'EIH VAT COLORS Chester Albert Amick and Roy Herman Kienle, Bound Brook, N. 5., assignors to Amerlcan Cyanarnid Company, New York, N. Y., a corporation of Maine N Drawing. Application July 31, 1944,

Serial No. 547,512

6 Claims.

This invention relates to new color compositions, to printing pastes prepared for use in printing on textile fabrics, paper and the like and to products printed therewith.

Use of printing-color pastes containing dyes, particularly in printing operations using vat dyes, is sufficiently well-known so that the procedure has become almost standardized. The actual color source may be either a dye paste or a dye powder. In addition to the real color, a dye paste usually contains agents to prevent drying-out, settling and/or freezing. Dye powders, not being subject to these difficulties, do not require these agents but they usually contain agents or are so processed as to promote dispersibility.

In either case, the dye paste or dye powder must be admixed with suitable thickener, usually a gum dispersion, to form a printing-color paste which is suitable for application. In the case of vat dyes, it is also necessary to add a reducing agent and usually an alkali. Because the color yield from a printing-color paste often decreases rapidly and the paste usually become too stiii for use as the paste ages after being made up, they are ordinarily prepared by the fabric finishers just before they are to be used.

However compounded, the printing-color pastes are then applied to textile, paper or other fabric materials for decorative or protective purposes. Subsequently, the printed pieces are dried, aged in a steam ager, treated with an oxidizing agent, rinsed and finally dried. Usually in processing textiles, the printed fabric also is soaped at or near the boil with about a 0.1% soap solution and again rinsed before the final drying operation.

In making up and applying printing-color pastes it has been found that a material suitable for use as a printing assistant is of advantage in obtaining maximum color yield. The exact way in which these materials act to produce an improved color yield in printing is not entirely understood. It is with color compositions containing such printing aids or assistants that the present invention is particularly concerned.

Although printing aids are desirable in the printing-color pastes, the exact point at which they are added may vary. Dye pastes may contain printing aids as one of their components and printing-color pastes made therefrom will obviously contain the printing assistant. Where a, printing assistant is not present in the dye paste, it may be added at the time of making up the printing-color paste.

It is preferable, however, that the printing assistant be incorporated in the actual dye paste.

Their addition at the proper point in theg'm'andfacture of the paste is not only easier, but in addition they are thus generally more uniformly dispersed throughout a printing-color; paste made therefrom. A a result, the printingassistants usually operate more effectively when'the printing-color paste is finally applied totlie fablric. ,1

It is only relatively recently that dye powders suitable for use in making up printing-color pastes have been available. Most of the printing ample, triethanol amine; and/or polyhydric jalcohols such as glycerine, glycol, diethylenegly'col and the like. Various derivatives therefrom also have been tried. When a printing aid" is to be incorporated in a dye powder, a solid is necessary. Examples of such solids which have beenfuse'd in the past include the 'hydrochlorides of alkylol amines; silver salt (sodium anthraquinone betasulfonate) anthraquinone and certain metal salts such as those of cobalt and'iron. J I

Unfortunately, most of these printing aids previously used are not as satisfactory as may be desired. Many of them will not in all cases produce the intensification of color for which they i were intended. Others, such as polyhydric alcohols, cause deterioration of'the printing-color pastes so that marked variations in the strength of prints therefrom are observable even after the printing-color paste has been allowed t stand for only a relatively short time. Many of them are satisfactory with some colors but have an adverse effect on others, even to the extent of visibly altering the shade. Noneofthfim' are suitable without modification for use both in paste and powder compositions.

There remains, therefore, a demand for suitable color compositions which will produce a satisfactory coloration when made into printing pastes and printed on the material but which are not subjectto diiilculties from deterioration or setting of the composition on standing. Preferably also, the color composition should be capable of derivation from either dye pastes or dye powdam and the printing therefore be obtainable in dry powdered form.

therefrom.

7 be variedover a considerable. range.

generic formula assistants used should In addition, they should be readily available or cheaply and easily prepared. Therefore, the

principal. objects of the present invention are to find suitable printing assistants and to combine them into color compositions and printing pastes.

In general these objects are accomplished using as printing assistants the combination of urea or a substituted urea and a monoquinonyl amide of a dicarboxylic acid represented by the general formula V 7 H H II p QN-CAc-COX V for satisfactory use.

saturated acids such as malonic, succinic, glutaric,

in which Q represents'a quinonyl radical, Ac

represents the residue of a cyclic or aliphatic dicarboxyllc acid, and X represents hydrogen or an alkali metalradicall 'Sofar-as the present invention is concerned,

the assistants may be, added to theprinting- -color.

pastes in any ,of several ways during the compounding of the latter. They may be incorporated into the thickener; into the dye pastes or dye powders or they maybeblended directly into the printing-color paste. However, as pointed out above, it is preferable that they be incorporated .in the dye paste or powder during manufacture.

Use of these materials in the. colorcompositions of the present invention has a number 'of advantages. Both of the compounds used are dry solids. Both areeither soluble or dispersible in dye-paste suspensions- They have, therefore, a general application since they may be' incorporated into either dye pastes or dye powders. They do not cause deterioration of printing-color pastes on standing. They tend to prevent setting up. of the he acids may be either adipic, azelaic, sebacic, and the like or unsaturated acids such as maleic, fumaric, and the like.

As pointed out in connection with the'generic formula, Q represents a quinonyl' group. Ordi- V 'narilyhowever,Qwill be limited to the beta-naph 3V 4 thoquinonyl and the alpha and beta'anthrae quinonyl radical. Alpha-naphthoquinone appears to transform to the beta derivative in forming the amide. The invention however is not necessarily so limitedsincelquinonyl radicals having various substituents on the ring maybe used.

The exact function of the urea or substituted urea and its mode of operation is not fully understood. There, is apossibility 'that'there is an' association between it and the monoquinonyl amide which breaks down under conditions of use as well as that the two remain separate entities. In any case, however, the result obtainedis far superior to that obtained by the useof either alone, or would alone. V

Urea itself, being the'niost readily available of the ureas is probably preferable for use in the be expected from the use'of either compositions of the present invention; -Parti-" cularly is this true sinceit produces wholly sat isfactory color yields and its other physicalprop erties are satisfactory. The invention, however,

is not limited thereto. Substituted ureas, parti cularly the alkyl and alkylol ureas in whichthe substituent group contains up to about six-carbon atoms, phenyl urea, guanyl urea and dicyandiamide may be used effectively if so desired...

In using urea, or substituted ureas, it is often preferable to colloidize the urea for ease in hand- .ling and it insure thorough dissemination. This.

' is quite simply carried out by'thoroughly mixing printing paste. They encourage the production of excellent color yields, even under hot ageing conditions.

water or alchol, producing excellent color. yields whatever the mode of admixture.

In preparing the amides tobe used in the pres ent. invention, the dicarboxylic acid froin' which they .are derived may be-quite varied. ,Suitable acids include both cyclic and/or aliphatic dicar- Their use is simple since they may be. employed as either powders oras suspensions in boxylic acids. Of the cyclic dicarboxylic acids,

.phthalic acid is perhaps the most common and its ginal aliphatic acid is "considered .to have the i n th e fliheh iq 1 m have e bstantially any value iromlzerd as in oxalic 'acid,.to aboutr eight; However, wherefy is. greater; than about siX, difficulties are ecouritered' ini preparing the derivativesQ f 'A bove about y=8, there-is a,-

tendency for the compounds to be too insoluble If the orione part of urea and about three parts of dextrin, j preferably yellow corn dextrin with .a small amount of water in a Banbury mixer or the like. The resultant product is then vacuum dried "at about 60-70 C. and ground to about minus 140.- mesh. When colloidi'zed in this manner, therurea 7 is particularly well adapted for use in powder compositions.

, While the dye and printing paste compositions" of. the present invention are not limited to the V 7 use of any particular dyes or dye forms, they are especially suitable for use with vat-dyes in either paste or powder form. Particularly goodresuits may be obtained using vat-dye powders of high auto dispersibility as set forth in Crossley et al.,

United States Reissue Patent 21,409, reissued -March 19, 1940. By combining thecolormaterials of that patent into the compositions of the pre ent invention, the full advantages of both may be gained with a resultant simplicityin use andex-f cellence of shadeand sharpness of color. 1 Printing pastes made in this way havethe particular advantage that the dyes remain-in a highly' dispersed state as individual particles I rather than as dispersions. of particle aggregates-- In the present specification and claims,where highly-dispersed dyes are referred to, reference 1 to pastes in which the dye particles are so dispersed is intended. I k The invention willbe more fully setforth in connection with the following examples which are intended to be illustrative-and not by way flimi- I tation; All parts are by Weightunless otherwise 1 'noted.

. In the succeeding examples, testprints'qwere made on two differenttypes of fabrics. when rayon is referred to, a titanium-dioXidepig--- C. Those ageings referred to as plant or hot ageings were carried out in the temperature range of about 106-110 C. In the case of the cotton prints ageing periods of 3 minutes, minutes or both were used. On rayon, ageing periods of 5 to minutes or both were used. The shortest period which gives a satisfactory ageing ispreferable.

Example 1 A paste was prepared by slurrying 2,-000 parts of 177 British gum (Stein Hall) in 5,000 parts of water and the mixture was heated with continuous stirring until the temperature reached about 185 C. Heating was continued for about 1 hours after which 450 parts of powdered sodium carbonate and 450 parts of powdered potassium carbonate were added and the mixture stirred until the carbonates dissolved. Heating was discontinued but stirring was continued until the temperature reached approximately 150 F. at which time 700 parts of sodium sulfoxylate formaldehyde were dissolved therein. Subsequently, 600 parts of glycerine were added and the paste bulked to about 10,000 parts. Stirring was continued until the paste cooled to room temperature. In the succeeding examples this paste is referred to as thickener A.

Example 2 720 parts of 3-2 British gum and 720 parts of KAC-4 gum (Stein Hell) were added to 5,600 parts of water and heated over a steam bath for approximately hours after the temperature reached 185-190 F. The source of heat was then removed but stirring was continued until the temperature decreased to 120 F. at which time 1,200 parts of potassium carbonate which had been previously dissolved in 1,000 parts of water was added to the cooked gum. 1,560 parts of sodium sulfoxylate formaldehyde were dissolved in 1,500 parts of water at a temperature of about 140 F. and added to the common mixture with stirring until the whole was thoroughly mixed. 360 parts of glycerine were then added and after thorough stirring the whole was bulked to 12,000 parts. In the succeeding examples this mixture is referred to as thickener B.

Example 3 48 parts of Orange R (Color Index 1217) presscake containing 12 parts real color were diluted with 52 parts of water to make a uniform suspension. 10 parts of this color suspension, 5 parts of a 6% slurry of the alpha-anthraquinonyl mono amide of maleic acid and 5 parts of water were intimately mixed, after which 80 parts of thickener A were added. This printing color paste was used as the control. To a second 10 parts of the Orange R slurry were added 5 parts of a 6% suspension of the alpha anthraquinonyl mono amide of maleic acid and 5 parts of urea, after which 80 parts of thickener A were added.

Both color pastes were then printed on pigmented (TiOz) viscose rayon and on 80 x 80 bleached, unmercerized cotton print cloth, dried in a hot air dryer at a low temperature, aged in a steam ager, treated with an oxidizing agent, rinsed, soaped in a 0.1% soap solution for 5 minutes at the boil, again rinsed, and ironed dry.

Prints made from the paste containing the urea are stronger and brighter than the prints made from the prints made from the paste in which no urea was used.

Example 4 The procedure of Example 3 was repeated exactly, except that a 6% suspension of the betaanthraquinonyl monoamide of maleic acid was used in place of the alpha-anthraquinonyl monoamide. Prints made from the paste containing urea and the beta-anthraquinonyl mono-amide of the maleic acid were bright and appreciably stronger than those made from the paste containing no urea.

Example 5 The procedure of Example 3 was again repeated exactly except that the beta-anthraquinonyl monoamide of phthalic acid was used in place of the beta-anthraquinonyl monoamide of maleic acid. Bright, strong prints are obtained when the urea was used and the ageing is carried out at a temperature of about 108 C. These prints are stronger than those obtained when no urea is used.

Example 6 The procedure of Example 3 was repeated except that the alpha-anthraquinonyl monoamide of succinic acid was used in place of the alpha- 'anthraquinonyl monoamide of maleic acid. The

results were essentially those obtained in Example 3 being better than when no urea is used.

Example 7 The procedure of Example 3 was repeated except that the alpha-anthraquinonyl monoamide of fumaric acid was used instead of the alphaanthraquinonyl monoamide' of maleic acid. Again the addition of urea caused improved results to be obtained.

Example 8 Again the procedure of Example 3 was repeated except that the alpha-anthraquinonyl monoamide of maleic acid was replaced by the betanaphthoquinonyl monoamide of maleic acid. Substantially duplicate prints of those of Example 3 were-obtained.

Example 9 A Vat Yellow GC presscake (Color Index 1118) was slurried with water to give about a 10.5% suspension. The procedure of Example 3 was repeated exactly using the Yellow GC color instead of the Orange R. The print from the paste in which the urea was present was stronger and fuller than the print obtained from the paste in which no urea was used, particularly in commercial-type ageing.

Example 10 The procedure of the preceding experiment was repeated exactly except that thickener B was substituted for thickener A. The results were essentially the same, the paste containing urea giving a stronger and fuller color value than the paste in which no urea is present.

Example 11 The procedure of the preceding Example 9 was repeated exactly except that 10 parts of a Vat Navy Blue aqueous dispersion (Color Index 1100) containing about 1.8 parts of real color is used in place of the Vat Yellow GC. The prints made 'from'the paste containing'the urea were stronger and brighter than those. made from which no urea was present.

the'paste in Example 12 V v I B'parts of a dispersible Orange R powder (Color Index 1217) prepared according to U. S. Reissue Patent 21,402 and containing about 1.2 parts of real color, were dry blended with 0.3 part of the alpha-anthraquinonyl monoarnideof maleic acid. 11.7 parts of water were added to this and intimately mixed. 85 parts of'thickener B were added and after mixing to form a smooth paste, was'used as the control sample. A second printing paste was prepared by using 3 parts of the same color, and dry blending therewith 0.3 part of the alpha-anthraquinonyl monoamide of maleic acid and 5 parts of urea. To this was added 8.7 parts of water and after thorough mixing '85 parts of thickener B were added thereto.

These color pastes are then printed and finished as in Example 3. Prints made from the paste in which both the alphaeanthraquinonyl monoamide of maleic acid and urea were present were defi nitely stronger and brighter than those obtained fromthe pastes in which'no urea was used.

Example 13 Again the procedure of Example 12 was repeated except that 20 parts of colloidized urea (prepared from urea and dextrin is a 1:3 ratio) were substituted for the 5 parts of urea. The dry blending operation was more easily carried out. Prints obtained from both the control sample and that containing the colloidized urea were substantially the same as those of Example 11' although on the rayon sample the color yield was slightly improved by using colloidized urea.

We claim:

1. A color composition comprising essentially a vat-dye, a quinonyl monoarnide of a dicarboxylic acid, the quinonyl radical being selected from the group consisting of the beta-naphthaquinonyl and alphaand beta-anthraquinonyl radicals, and

a urea.

2. A dye powder composition comprising essentially-av dry vat dye powder of highautodls- 'alphaand beta-anthraquinonyl radicals, and a .persibility, a drypowdered quinonyl monoamide of a dicarboxylic acid, the quinonyl radical'being selected from thegroup consisting of the betanaphthaquinonyl; and alphaand beta-anthra quinonyl radicals, and a drypowdered urea.

, 4. A dye powder composition comprising essentially a dry vat-dye powder of, high autodispersibility, a dry. powdered quinonyl monoamide of .a dicarboxylic acid, the quinonyl radical being selected from the group consisting of the beta-naphthaquinonyl and alphaand betaanthraquinonyl radicals, and a dry powdered urea colloidized with dextrin in the ratio of about 1 :3.

5. A printing-paste composition comprising essentially a thickener, a vat-dye, a quinonyl ,monoamide of a dicarboxylicacid; the quinonyl radical being selected from the group consisting of the beta-naphthaquinonyl and alphaand beta-anthraquinonyl, radicals, and a urea. ,6. Amethod' of printing with vat color which comprises printing with aprinting paste composition comprising essentially a thickener, a vatdye, a quinonyl monoamide of a dicarboxylic acid, the quinonyl radical being selected fromthe group consisting of the betanaphthaquinonyl and urea. I r 1 CHESTER ALBERT AMICK.

ROY

REFERENCES CITED;

The following references are file of this patent 7 I UmrED' sTATEs PATENTS Number 2,286,262 Clark June16, 1942 of record in the 

